Process of preparing vat dyestuffs



Patented May 3, 1932 P A T T FFICE GEORG KRANZLEIN, MARTIN GORELL, ANDHEINRICH VOLLMANN, F FRANKFORT-ON- THE-MAIN-HOCI-IST, GERMANY, ASSIGNORSTO GENERAL ANILINE WORKS, INC., 0]? NEW YORK, N. Y., A CORPORATION OFDELAWARE PROCESS OF PREPARING VAT DYESTUFFS No Drawing. Applicationfiled May 3, 1929, Serial No. 360,327, and. in Germany May 2, 1928.

The present invention relates to new vat dyestufis of the3.4.8.9-dibenzpyrene-5.10- quinone series and to a process of preparingthe same.

WVe have found that halogenated 3.4.8.9-dibenzpyrene-5.l0-quinones areconverted into clearer and faster vat dyestufis by treating them with analkaline oxidizing agent, for instance with sodium hypochlorite. The

dyestufis thus obtained have more valuable properties than the dyestuffsnot treated with an alkaline oxidizing agent. They possess, forinstance, in general a higher fastness to washing.

The following examples serve to illustrate our invention but they arenot intended to limit it thereto, the parts being by weight.

1. 40 parts of pure 8.4.8.9 dibenzpyrene- 5.10-quinone (crystallized forinstance from nitrobenzene) are dissolved in 400 parts of chlorosultonicacid to which some iodine has been added; At a temperature of from 85 C.to 90 C. 44 parts of bromine are added drop by drop and the solution isthen heated for 12 hours. After the mass has been in troduced intowater, filtered by suction and washed until neutral, the press-cakeformed is suspended in 1000 parts of Water and 200 parts of an alkalinesodium-hypochlorite so lution and heated on the water bath for about 3to 4 hours, while well stirring. During this operation the tint of thedyestufi becomes clearer. The dyestuff, after being worked up in theusual manner, has the following formula: V

It dissolves in concentrated sulfuric acid to a reddish-blue solutionand dyes cotton from $5 a red vat bright golden-orange tints.

2. parts of pure 3.4.8.9-dibenzpyrena 5.10-quinone are dissolved in 400parts of chlorosulfonic acid to which 2 parts of sulfur have been addedand into this solution a current of chlorine, being as constant aspossible, is introduced for 15 to 20 hours at a temperature of between85 C. and 90 C. Thereupon the solution is poured into water and workedup in the usual manner. The isolated dyestutt is suspended in 1000 partsof water and about 300 parts of an alkaline sodium-hypochlorite solutionand heated on the water bath for 3 to 4 hours, while well stirring. Thedyestufl', after being worked up in the usual manner, has theconstitution of a dichloro-dibenzpyrene-5.10-quinone, dissolves inconcentrated sulfuric acid to a reddish-blue solution and dyes thevegetable fiber from a red vat bright yellow tints of ex cellentfastness properties. It possesses most probably thefollowing structuralformula:

IO-quinone are dissolved in 400 parts of chlorosulfonic acid to whichabout 2 parts of iodine have been added. At a temperature of90 C. 22parts of bromine are added drop by drop and the solution is then heatedfor about 20 hours. After'the mass has been introduced into water,filtered by suction and washed until neutral, the press-cake formed issuspended in 1000 parts of water and 200 parts of an alkalinesodium-hypochlorite solution and heated on the water bath for about 3 to4 hours, while well stirring. During this operation the tint of thedyestuff becomes clearer. The dyestuff worked up in the usual manner isidentical with that obtained according to Example 1.

4:- 40 parts of pure 3.4.8.9-dibenzpyrene- 5.10-quinone are dissolved in400 parts of chlorosulfonic acid to which 4 parts of sulfur have beenadded and chlorine is introduced into the solution at a temperature ofabout 95 C. until its amount has reached the weight necessary for thedichlorination. Thereupon the mass is poured into water and worked up inthe usual manner. The isolated dyestuff is suspended in 1000 parts ofwater and about 300 parts of an alkaline sodium-hypochlorite solutionand heated on the water bath for 3 to 4 hou'rs,while well stirring. Thedyestufi worked up in the usual manner is identical with that obtainedaccording to Example 2.

5. 19 parts of bromo-3.4.8.9-dibenzpyrene- 5.10-quinone (obtainedaccording to Example 1) are dissolved in 500 parts of chlorosulfonicacid while stirring, 1 part of iodine is added and chlorine isintroduced at between 80 C. and 90 C. in such amountvthat the weight ofthe solution is increased for 15 to 20 parts. After the pure bluesolution of chlorosulfonic acid has been poured into 500 parts ofconcentrated sulfuric acid, the mass is poured on ice. The dyestuffwhich separates in the form of yellow flakes is isolated in the usualmanner. Thereupon the dyepaste is suspended in-2000 parts of water and200 parts of an alkaline sodium-hypochlorite solution and, heated on thewater bath for 2 to 3 hours, while stirring- During this oper- I ationthe tint of the dyestuff becomes clearer.

The pure dyestufi' thus obtained crystallizes from nitrobenzene in theform of yellow needles and dyes the vegetable fiber from a violet vatfast yellow tints. It possesses most probably the following formula:

sodium-hypochlorite solution, a dyestuflf is obtained which dyes thevegetable fiber from a violet-red vat yellow tints of the shade of theunsubstituted 8.4.8.9-dibenzpyrene-5.10- quinone. It possesses mostprobably the following structural formula:

The alkaline sodium hypochlorite solu tion used in the precedingexamples contains 8-'12% of active chlorine.-

lVe'Claim:

1. The process which comprises heating a halogenated 3.4.8.9dibenzpyrene-5.10-quinone with an alkaline sodium hypochlorite solutionat between about 90 and 100 C.

' 2. The process which comprises heating a di-halogenated 3. 1.8.9dibenzpyrene- 5.10- quinone -withan alkaline sodium hypochloritesolution at between about 90 and The process which comprises heating adi-bromo 3.4.8.9-dibenzpyrene-5.10-quinone with an alkaline sodiumhypoohloritesolution at betweenabout 90 an'd 100 0.

1.- The process which comprises heating a di-bromo 3.4.8.9dibenzpyrene-5.10-quinone with an' alkaline sodium hypochlorite solu-'tion at between about 90 and 100 C. for about 3-4hours', while stirring.a

5. As new compounds; the dyestufis obtainable byheating ahalogenatedBABQ-dibenzpyrene-5.10-quinone with an alkaline-sodiumhypochloritesolution at between-about 90 and 100 C.,'the said dyestuffsbeing substantially pure products and being characterized-by clear tintsand a high fastness to washing) I I 6. As new compounds, the dyestufisobtainable by heatinga di-halogenated 3.1.8.9- dibenzpyrene-5.10-quinonewith an alkaline sodium hypochlorite solution at between about 90 and100 6., thesaid dyestuifs being substantially purep'roductsand beingcharacterized by clear tints and a high fastness to washing. a

7. As new compounds, the dyestuifs obtainable by heating a 'di-bromo3.4.8.9-dibenzpyrene-5.10-quinone with analkalinesodium hypochloritesolution' 1 at between about 90 and 100 C. for about 3-4 hours, whilestirring, the said dyestuffs dissolving in concentrated sulfuric acid toa reddish-blue solution and dyeing cotton from a red vat 5 brightgolden-orange tints of high fastness to washing.

8. As a new compound, the dyestufi obtainable by heating adibromo-3.4.8.9-dibenzpyrene-5.10-quinone of the following formula:

with an alkaline sodium hypochlorite solution at between about .90 and100 C. for

about 3-4 hours, while stirring, the said dyestuff dissolving inconcentrated sulfuric acid to a reddish blue solution and dyeing cottonfrom a red vat bright golden-orange tints of high fastness to washing.

9. As a new compound, the dyestufi' obtainable by heating adichlor-3.4.8.9-dibenzpyrene-5.lO-quinone of the following formula:

with an alkaline sodium hypochlorite solution at between about 90 and100 C. for about 3-4; hours, while stirring, the said dyestufidissolving in concentrated sulfuric acid to a reddish blue solution anddyeing cotton from a red vat bright yellow tints of high fastness towashing.

In testimony whereof, we aflix our signatures.

GEORG KRANZLEIN. MARTIN CORELL. HEINRICH VOLLMANN.

